Etherified methylolated melamines and process for finishing cellulosic textile material therewith



United States Patent "'ce 3,519,625

Patented July 7, 1970 aminoplast resins on cellulosics, it is extremely undesir- 3,519,625 able to have the use of the resin for its purpose, restrict ETHERIF D METH MELAMINES AND the functioning of the dye for its purpose. It is therefore IFA TIL ggg cggTlg an object of the present invention to provide a means of treating direct-dyed cellulosics with aminoplast resins Michael Thomas Beachem Somerset and Frederic Hough- 5 ton Megson Martinsvflle NJ assignors to American whereby crease resistance is imparted to the cellulosic with no substantial reduction in lightfastness. It is a fur- 332%}: Company Stamford Conn" a corporatmn ther object to provide cellulosics which have been direct No Drawing. Filed Mar. 13, 1967, Ser. No. 622,400 dyed and have improved lightfastness, while also exhibit- Int. Cl. C07d 55/22 10 ing good crease-resistance by virtue of treatment with a 5 Claims particular aminoplast resin textile improving agent. Other objects will be apparent from the ensuing description of this invention.

It has now been discovered in accordance with this in- ABSTRACT OF THE DISCLOSURE 15 vention that etherified methylolated melamines of For- This invention relates to new and etherified methylmula I impart crease-resistant properties to cellulosic texoleated melamines and their use on cellulosic textile matile materials without adversely affecting the lightfastness terials dyed with direct dyes. The new etherified melaof such material dyed with direct dyes. This is a surprismines impart crease-resistance to such materials and the ing discovery since cellulosics dyed with direct dyes are light-fastness of the direct dyes is improved. normally adversely afiected as to lightfastness when aftertreated with aminoplast textile finishes.

The textile finishing aminoplast resins used in this invention are applied to direct-dyed cellulosic textile ma- This invention relates to new compounds and to textile t i l b tandard procedures, as by dipping, padding, finishes for dyed cellulosic textile materials. More parspraying, etc., and the finishes are converted to an inticulafly, it relates to etherified m r hy e soluble state by heating the treated fabrics in the presence precondensates and their use on cellulosic textile mateof a atalyst, The dyed materials thus treated exhibit rials dyed with direct dyes. Still more particularly, it crease-resistant. and wrinkle-recovery properties, and a relates to the use of new etherified methylolated melalightfastness equal to, or even better than the untreated, mines of the Formula I: 3 dyed material.

compounds of Ifil N /CH2O-a1ky1+ M00112- Formulal MX (a1kyl-OOH2)zN-O b-N\ III N crux N(CH Q a1k 1) The compounds of Formula I can be made by reacting I an N-halomethylmelamine of Formula II with an alkali metal salt of Formula III as above: N

g N CH2O alkyl wherein X is chlorine or bromine, M is an alkali metal, (alkyl-OOHzhN- and alkyl and R are as defined above for Formula I. N CHz-OCHz- The compounds of Formula II and a process for their manufacture are disclosed and claimed in US. Pat. No.

' (1) 3,317,529, issued May 2, 1967 to Beachem et al. wherein alkyl is a lower-alkyl group (1-4 C atoms) and Representative N-halomethylmelamines of Formula II R is hydrogen, alkyl of up to 18 C atoms, phenyl or which can be used in this invention include N-chlorophenyl(lower-a1kyl), any of the phenyl or said R groups, methyl N,N',N,N",N"-pentakis(methoxymethyl)2,4,6-

especially when R is aryl, having up to two inert radicals, triamino-s-triazine, N-bromomethyl-N,N,N,N",N"-pensuch as lower-alkyl and lower-alkoxy groups. takis(methoxymethyl)-2,4,6-triamino-s-triazine, N-bromo- The use of aminoplast resins to impart crease-resistance methyl N,N,N,N",N" pentakis (ethoxymethyl)-2,4,6- to cellulosics is well-known. These resins perform their triamino-s-triazine, N-chloromethyl-N,N',N',N",N"-penfunction economically and efiiciently without adversely takis(butoxymethyl)-2,4,6-triamino-s-triazine, etc. affecting many of the other desirable properties of cellu- Representative compounds of Formula III include the losics, such as, for example, fabric hand, soil resistance sodium salts of benzyl alcohol, p-methylbenzyl alcohol, or fabric durability. However, aminoplast resins do in p-ethylbenzyl alcohol, etc. some cases have an adverse effect on color stability of The reaction of compounds of Formula II with comdyed cellulosics. Thus, it is well-known that aminoplast pounds of Formula III is carried out with or without a crease-preventing finishes can cause accelerated fading of solvent, although it is preferable to use a solvent, parmany direct dyes, i.e., the lightfastness of cellulosic texticularly the alcohol from which the said alkali metal salt tile material dyed with direct dyes is often reduced when is prepared. The reaction is conveniently carried out at the dyed material is after-treated with an aminoplast resin room temperature, although any temperature between or reactant, such as a urea-formaldehyde or a melaminethe freezing and boiling points of the reaction mixture formaldehyde condensate. Commercial resins which have may be used. Equimolar amounts of reactants can be adbeen shown to cause fading of certain direct dyes include vantageously used, although an excess of either can be hexa(methoxymethyl)melamine, polymethylolurea with present without adverse effect.

slight degree of methylation, blends of partially methyl- The cellulosic textile materials include fibers, threads, ated hexamethylolmelamine and urea-formaldehyde reacyarns, knitted and woven cloth as well as non-woven tion products, and methylated trimethylolmelamine. fabrics and felted materials. These cellulosic materials In view of the widespread use of both direct dyes and will normally contain at least 50% cellulosic fibers, such 3 as cotton, viscose, cuprammonium rayons, linen, hemp, jute and ramie, either alone or mixed with themselves or other fibers.

The cellulosic textile materials will be dyed with the class of azo dyes known as direct dyes and so classified in the Color Index, second edition. Such dyes are characterized as anionic dyes having affinity for cellulosio fibers when applied from an aqueous dyebath containing an electrolyte. They are mainly azo dyes containing sulfonic acid groups as the sodium salts. Representative direct dyes are Direct Yellow 6 (0.1. 4001), Direct Yellow 11 (CI. 40000), Direct Orange 26 (Cl. 29150), Direct Red 1 (CI. 22310), Direct Red 31 (C.I. 29100), Direct Blue 2 (Cl. 22590), and Direct Green 1 (0.1. 30280).

The dyed materialsrare treated with the textile finishes of this invention using aqueous or organic solvent solutions or dispersions which can be applied by spraying, dipping or padding according to well-known procedures. Between 0.5% and 40% solutions or dispersions are normally used. The amount of finish on the textile material can be varied, usually between 0.5% and 40% based on the Weight of the textile material, with amounts between 2.5% and 15% preferably being used for practical crease-resistant and Wrinkle-recovery properties. The treated fabrics are dried and then heated, preferably in the presence of a catalyst, to efifect insolubility of the precondensate on the fabric (cross-linking, etc). Curing temperatures between 275 and 400 F. for periods of about 20 minutes to 30 seconds are normally used.

Suitable catalysts includes those normally used for melamine-formaldehyde condensates and their etherates. These include the metal salts such as magnesium chloride, zinc nitrate and zinc chloride, ammonium salts such as ammonium sulfate, ammonium chloride, and organic amine hydrochlorides. In the case of magnesium chloride, the amount is between about 4.5% and 24%, preferably between 9% and 15%, of the anhydrous salt based on the weight of the precondensate.

The treated dyed fabric obtained by this convention will be found to have good wrinkle-recovery and creaseresistance normally required for commercial cellulosics. In addition, advantageously, they will be found to possess lightfastness not previously attained with fiJII'liIlOPlELSt resin-treated direct-dyed cellulosics.

The following examples are presented to further illustrate this invention.

EXAMPLE 1 N C H2 OHzCaHs A solution of 39.8 parts (0.01 mole) of N-chloromethyl N,N',N',N",N" pentakis(methoxymethyl-2,4,6= triamino-s-triazine in 54.1 parts (0.50) mole of benzyl alcohol is added slowly to the reaction mixture of 54.1 parts (0.50 mole) of benzyl alcohol and 2.39 parts (0.105 mole) of sodium at 2530 C. After a reaction period of about 24 hours, 100 parts of water is added. The organic layer is washed with 10% aqueous sodium hydroxide, sodium chloride solution and a 50:50 (by volume) mixture of methanol and water. The unreacted benzyl alcohol is removed by vacuum distillation. The product, a viscous liquid, is N-(benzyloxymethyl-N,- N,N,N,N"pentakis (methoxymethyl)-2,4,6-triaminos-triazine.

N CHzO CzHs b-N N CHzO-CHz-CuHa- 14(1 The procedure of Example 1 is followed, substituting an equivalent amount of p-methoxybenzyl alcohol for the benzyl alcohol. The product is N-(p-methoxybenzyloxymethyl) N,N,N',N",N-pentakis(methoxymethyl)- 2,4,6-triamino-s-triazine.

EXAMPLE 4 N(CH2O CH3):

CHQO CH (C1130 CHzhN- -N CHzO-CH2*CsHr-C2H5(D) The procedure of Example 1 is followed, substituting an equivalent amount of p-ethylbenzyl alcohol for the benzyl alcohol. The product is N-(p-ethylbenzyloxymethyl)-N,N',N,N",N-2,4,6-triamino-s-triazine.

EXAMPLE 5 Pad baths are prepared containing 6.25 of precondensate solids and 12% magnesium chloride based on the precondensate solids in the bath.

Pad Bath A N (benzyloxymethyl) N,N',N,N",N", pentakis- (ethoxymethyl)-2,4,6-tria-mino-s-triazine, the product of Example 1, in 85% aqueous dimethylformamide.

Pad bath B N,N,N,N,N,N" hexakis(methoxymethyl) 2,4,6- triamino-s-triazine in water, for purposes of comparison.

The pad baths are applied to x 80 cotton percale at 5% O.W.F. of precondensate solids by standard padding procedure using 80% Wet pickup. The treated fabrics are dried for 2 minutes at 225 F. and the finish is cured by heating the fabric at 350 F. for 1.5 minutes.

The wrinkle recovery of the treated fabrics and a sample of untreated fabric is measured on a wrinkle recovery tester following tentative test method 66-1959T, described on page B-l43 of the 1964 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists.

The strength loss due to retained chlorine is measured by standard test method 924962, described on page B-102 of the above reference, before and after five acid rinses.

The acid rinses (acid sours) are carried out by immersing the fabric in an aqueous solution of zinc fluorosilicate followed by drying. v

The measurements of finishes A and B corresponding to pad baths A and B, respectively, show the finishes to be about equivalent in degree of wrinkle recovery, but

CH2OCH3 that finish A is superior to the other finish in resistance to damage caused by retained chlorine after five acid rinses.

EXAMPLE 6 Pad baths are prepared containing 6.25% precondensate solids and 12% magnesium chloride based on the precondensate solids in the bath.

Pad bath A N (benzyloxymethyl) N,N,N,N",N pentakis (methoxymethyl) 2,4,6 triamino-s-triazine product of Example 1) in acetone.

Pad bath B N,N,N',N,N",N" hexakis(methoxymethyl) 2,4,6- triamino-s-triazine in water.

The pad baths are applied to a sample of 80 x 80 cotton percale dyed with Direct Red 81 (CI. 28160) at 5% O.W.F. of precondensate solids by standard padding procedure using 80% wet pickup. The treated fabrics are dried for 2 minutes at 225 F., and the finishes are cured by heating the fabrics at 350 F. for 1.5 minutes. Also a sample of the dyed, but untreated, fabric is rinsed in water and dried. A portion of each of the fabrics of each color is washed in a home-style washing machine at 110 115 F. with water containing 0.25% of a commercial anionic surface active agent and 0.25% of sodium carbonate. The washed fabrics are dried.

Samples of the treated fabrics, both washed and unwashed, are exposed in a Fade-Ometer for 60 hours, The degree of fading of the exposed samples of fabric is measured as follows:

Spectrophotometric curves of the unexposed portion of dyed fabric and the exposed portion of dyed fabric are recorded for 21 wavelengths over the complete visual range. The spectrophotometric data are converted to colormetric data by means of a digital computer. Numerical expressions of color in terms of 3-dimensional color coordinates are thus obtained. The two sets of colorimetric data, i.e., one set for unexposed fabric and one set for the exposed fabric, are then converted into a single color difference (in NBS units) by the system of Wyszecki, J. Opt. Soc. Am. 53, 1318 (1963). The evaluation of the colorimetric data can be done by computer.

The single number color difference thus obtained can be considered in this instance to be strength ratio figures between exposed and unexposed fabric, negative numbers indicating loss in strength, i.e. fading. The larger the color difference number, the greater the difference in the visual appearance between the two samples.

It is generally accepted that a color difference of 0.2 NBS unit is the minimum detectable amount which an experienced person can detect between two samples. The color difference for an acceptable commercial match is probably between 1.0 and 2.0 NBS units as discussed in the monograph by Judd, Color in Business, Science and Industry, Wiley, New York, 1952.

The results of the fading measurements are shown in Table I, finishes A and B corresponding to pad baths A and B, respectively.

TABLE I.-FADING IN NBS UNITS Initial Washed FinishA 7.0 11.1 Finish B -12. 6 16. 7 Untreated 10. 3 11. 3

TABLE I.-FADING IN NBS UNITS Initial Washed Finish A -7.0 11. 1 Finish B l2.6 -16.7 Untreated 10. 3 11. 3

It can be seen that finish A is superior to finish B in resistance to light-fading and is generally superior to the untreated dyed fabric.

We claim:

1. A compound of the formula:

wherein alkyl is an alkyl group of 1-4 C atoms and R is hydrogen, alkyl of up to 18 carbons or lower-alkoxy.

2. The compound according to claim 1 which has the formula:

3. The compound according to claim 1 which has the formula:

4. The compound according to claim 1 which has the ll (021- H2) 2NC 5. The compound according to claim 1 which has the formula:

Campbell et al.: J. Org. Chem., vol. 26, pp. 2786-9 1961 JOHN D. RANDOLPH, Primary Examiner I. M. FORD, Assistant Examiner US. Cl. X.R. 

